Tributylstannane → HCID 68183110, compound

HRID 1615569Notes

Reaction equation

[Cl:1][C:2]1[CH:7]=[CH:6][C:5]2[C:8]3([O:26][C:27](=[O:28])[C:4]=2[CH:3]=1)[CH:14](I)[CH2:13][NH:12][C:11](=[O:16])[C:10]1[S:17][C:18]([N:20]2[CH2:25][CH2:24][O:23][CH2:22][CH2:21]2)=[N:19][C:9]3=1.N(C(C)(C)C#N)=NC(C)(C)C#N.C([SnH](CCCC)CCCC)CCC>C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]2[C:8]3([O:26][C:27](=[O:28])[C:4]=2[CH:3]=1)[CH2:14][CH2:13][NH:12][C:11](=[O:16])[C:10]1[S:17][C:18]([N:20]2[CH2:21][CH2:22][O:23][CH2:24][CH2:25]2)=[N:19][C:9]3=1

Participants

Conditions

Temperature: 80 °C

Procedure

A solution of 5-chloro-7′-iodo-2′-(morpholin-4-yl)-6′,7′-dihydro-3H-spiro[2-benzofuran-1,8′-[1,3]thiazolo[5,4-c]azepine]-3,4′(5′H)-dione (0.0430 g, 0.0809 mmol) and 2,2′-azo-bis-isobutyronitrile (0.000664 g, 0.00404 mmol) in toluene (2.0 mL) was heated at 80° C. for 10 minutes, then added tri-n-butyltin hydride (0.0644 mL, 0.239 mmol) dropwise. The solution was stirred at 80° C. for 16 hours. The reaction was incomplete by LCMS and TLC, so added additional and 2,2′-azo-bis-isobutyronitrile (2 mg) and tri-n-butyltin hydride (0.050 mL) and stirred at 80° C. for 4 hours. The reaction mixture was cooled to room temperature and the solvent was evaporated. The residue was purified by preparative HPLC to give the product (0.0100 g, 31%). LCMS: (AA) ES+ 406, 408. 1H NMR (400 MHz, d6-DMSO) δ: 8.50-8.28 (m, 1H), 7.92 (d, J=2.0 Hz, 1H), 7.78 (dd, J=8.2, 2.0 Hz, 1H), 7.64 (d, J=8.2 Hz, 1H), 3.60-3.51 (m, 4H), 3.52-3.42 (m, 1H), 3.32 (m, 1H), 3.23-3.06 (m, 4H), 2.72-2.60 (m, 1H), 2.37-2.24 (m, 1H).

Workup

temperatureThe reaction mixture was cooled to room temperature
customthe solvent was evaporated
customThe residue was purified by preparative HPLC

Sources & evidence

ORD record: ord-50bdc3cebc544bb68b42cf667fa706e9
Source dataset: uspto-grants-2014_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08765746B2

Reaction notes

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